Vinyl resins plasticized with trisubstituted nitrilotripropionates



United States Patent F 3,278,478 VlNYL RESINS PLASTICIZED WITHTRISUBSTI- TUTED NITRILOTRIPROPIONATES James E. Masterson, Jenkintown,and David H. Clemens, Willow Grove, Pa., and Arthur W. Ritter, Jr.,Haddon Heights, N.J., assignors to Rohm & Haas Company, Philadelphia,Pa., a corporation of Delaware No Drawing. Filed Feb. 2, 1965, Ser. No.429,887 4 Claims. (Cl. 260--31.8)

This application is a continuation-in-part of application Serial No.296,461, filed July 22, 1963, now abandoned, which in turn is acontinuation-in-part of application Serial No. 269,855, filed April 2,1963, now abandoned.

This invention deals with trisubstituted nitrilotripropionates,processes for making these compounds, and resinous compositions. Thisinvention also deals With disubstituted iminodipropionates and processesfor making these compounds.

The trisubstituted nitrilotripropionates of the invention may berepresented by the formula:

oHzoI-nooow in which R represents a non-acetylenically unsaturatedhydrocarbon group. Typical thereof are ahe following: aryl, aralkyl,alkaryl, alkyl, and alkylene. Each of these groups generally has aminimum content of 6 carbon atoms and a maximum content of 18 carbonatoms;

R represents a non-acetylenically unsaturated hydrocarbon group. Typicalthereof are the following: aryl, aralkyl, alkaryl, alkyl, and alkylene.Each of these groups generally has a minimum content of 6 carbon atomsand a maximum content of 18 carbon atoms;

R represents a non-acetylenically unsaturated hydrocarbon group. Typicalthereof are the following: aryl, aralkyl, alkaryl, alkyl, and alkylene.Each of these groups generally has a minimum content of 6 carbon atomsand a maximum content of 18 carbon atoms.

It is preferred that the total carbon atom content of R R and R takencollectively, be no less that 20 carbon atoms and no more than carbonatoms.

The substituents R R and R need not all be the same; they may all bedifferent or two of the three substituents may be the same; all threemay be the same.

Typical of the substituents represented by R R and R are the following:2-ethylbutyl, n-hexyl, sec-hexyl, n-octyl, isooctyl, 2-ethylhexyl,2-ethylisohexyl, tert-octyl, isodecyl, n-decyl, stearyl, benzyl,palmityl, oleyl, monochlorobenzyl, dichlorobenzyl, nitrobenzyl,phenethyl, 6- phenylhexyl, and tetrahydrofurfuryl. Other substituentstypical of R R and R include mixtures of unsaturated and saturatedsubstituents derived from the selective reduction of vegetable andanimal fats and oils, such as tallow, soybean oil, safflower oil,linseed oil, and the like. They are commonly mixtures of palmityl,stearyl, oleyl, linoleyl, and linolenyl groups in various proportions,depending on the initial composition of the fat or oil and the degree ofselectivity of the reduction.

Typical of the trisubstituted nitrilotripropionates of the invention arethe following: trihexyl nitrilotripropionate, tri-Z-ethylhexylnitrilotripropionate, tri-n-octyl, nitrilotripropionate, triisooctylnitrilotripropionate, tri-n-decyl nitrilotripropionate, diisodecylnitrilotripropionate, tristearyl nitrilotripropionate, tripalmitylnitrilotripropionate, tribenzyl nitrilotripropionate,tritetrahydrofurfuryl nitrilotripropionate, t-riphenethylnitrilotripropionate, dioctylmonobutyl nitrilotripropionate,distearylmonobutyl Patented Oct. 11, 1966 ice nitrilotripropionate,tripentachlorobenzyl nitrilotripropionate, trioleylnitrilotripropionate, trioctenyl nitrilotripropionate, 11octyl-ndecyl(1.5-1.5)nitrilotripropionate, dihexylmonoctylnitrilotripropionate, and monohexyldioctyl nitrilotripropionate.

A particularly valuable group of the compounds of the invention is thetrialkyl nitrilotripropionates in which the alkyl groups may be all thesame or different.

The process for preparing the trisubstituted nitrilotripropionates ofthe invention comprises reacting an acrylate ester of the formula withammonia. In the above formula, R is as defined above. When a mixture ofacrylate esters is employed, the resulting trisubstitutednitrilotripropionates of the invention have R substitutents which aredissimilar. In the reaction of the invention, the molar ratio ofacrylate to ammonia should be at least 3 to 1. Generally, it ispreferred to use an excess of acrylate ester, preferably not exceeding10 mole percent, over the stoichiometric amount required, althoughhigher excesses are not detrimental.

The temperature at which the reaction proceeds may vary widely. It mayrange broadly from about 0 C. to the temperature at which the formationof the amide from the acrylate predominates over the addition reactionacross the double bond of the acrylate to form the ester. Generally, thetemperature is in the range of 5 to 150 C., and more preferably in therange of 30 to C. For best results, it is very advisable to continueheating the reaction mixture after essentially all of the ammonia hasbeen consumed. Usually heating is carried out at a temperature higherthan that at which the reaction between the ammonia and the acrylateester proceeds. Such heating temperature ranges from 50 to 100 C. orhigher. The progress of the reaction may be followed by thedisappearance of any intermediate disubstituted iminodipropionates thatmay be formed during the reaction. Such iminodipropionates may berepresented by the following formula 0 H 0 H 0 0 o R 011 01-1 0 0011(III) wherein R and R are as defined above in conjunction with thenitrilotripropionates.

In accordance with the invention, the reaction between the acrylateester and ammonia proceeds preferably in the presence of a solvent forthe ammonia. Typical solvents are: methanol, ethanol, propanol, butanol,dimethyl sulfoxide, dimethyl formamide, tetrahydrofuran, ethyleneglycol, dimethyl ether, 2-methoxyethanol, 2-butoxyethanol, anddiethylene glycol.

It has also been found that for best results the reaction is carried outin the presence of a catalyst selected from the group consisting ofsalts of alkaline and alkaline earth metals (metals from Groups IA andIIA of the Periodic Table) and compounds of the generic formula where RR R and R are hydrogen, alkyl, aryl, or aralkyl, and X is an anion whoseconjugate acid has a dissociation constant greater than 10- Examples ofcatalysts are the following: ammonium formate, ammonium acetate,ammonium butyrate, ammonium chloride, monomethyl ammonium chloride,monomethyl ammonium acetate, tributyl ammonium sulperiod and held atthat temperature for six hours.

fate, trioctyl ammonium iodide, tetramethyl ammonium butyrate,tetrabutyl ammonium acetate, tetrabutyl ammonium chloride, lithiumchloride, lithium acetate potassium chloride, sodium acetate, sodiumpr-opionate, sodium dichloroace-tate, magnesium acetate, strontiumtrichloroacetate, and the like. Preferably, the catalyst is soluble inthe reaction medium.

The catalyst is employed in catalytic amount, i.e., that amount whichincreases the speed of the reaction. Generally, an amount in the rangeof .05 to 5% of the total weight of the reactants is used.

The greatest benefits from the action of the catalyst are obtained byits presence in the reaction mixture from the time essentially all ofthe ammonia has been consumed. But, the catalyst may also be presentduring the reaction of the ammonia and the acrylate.

In a further embodiment of the invention, there is provided atransesterification process which comprises reacting trisubstitutednitrilotripropionates of the formula Ia /C HzCHzC O lower alkyl N-OHClfl C O 0 lower alkyl CHgCHzC O 0 lower alkyl (Ia) with at least onealcohol of the formula R OH (V) In Formula Ia above, lower alkyl istaken to mean an alkyl group of 1 to 4 carbon atoms. Preferably, thelower alkyl group is an alkyl group of 1 to 2 carbon atoms. In FormulaV, the R substituent may represent a nonacetylenically unsaturatedaliphatic hydrocarbon group. Typical thereof are the following: aralkyl,alkyl, and alkylene. These groups generally have a minimum carbon atomcontent of 6 atoms and a maximum carbon atom content of 12 to 18 with amaximum of 12 carbon atoms being preferred. In this embodiment of theinvention, the particular group which R represents is so selected as tobe different and of substantailly higher molecular weight than the loweralkyl groups in Formula Ia.

Alcohols typical of R OH are the following: n-hexyl alcohol,Z-ethylbutyl alcohol, n-octyl alcohol, isooctyl alcohol, 2-ethylhexylalcohol, n-decyl alcohol, 2-ethylisohexyl alcohol, isodecyl alcohol,stearyl alcohol, palmityl alcohol, benzyl alcohol, tetrahydrofurfurylalcohol, oleyl acohol, phenethyl alcohol, and others.

This embodiment of the invention provides a process for making, inessentially quantiative yields, trisubstituted nitrilotripropionates inwhich the alcohol moiety of the ester is of higher molecular weight thanthat of the acrylate ester by reacting ammonia and the acrylate esterand then reacting the nitrilotripropionate with an appropriate alcohol.

These alcohols may be used individually or in any mixture thereof. Wherethe alcohols are used in a mixture, the resulting trisubstitutednitrilotripropionates have R R and R which are different, the respectiveratios R R and R depending therefor on the particular ratio of alcoholsused.

At the end of the reaction, the product is purified by suitable methods,as by distillation, removal of excess reactants, such as the alcoholsand the acrylate.

As illustrative of the invention are the following examples. All partsare by weight unless otherwise noted.

The symbol Hg stands for mercury.

EXAMPLE 1 There are charged to a two-liter reactor parts of ammoniumacetate and 75.0 parts of methanol. There are added in portions over atwo-hour period 451.0 parts of methyl acrylate and 27.2 parts ofammonia. The temperature is raised gradually to 70 C. over a one-hourThe product is stripped of volatile materials to a temperature of 100 C.at 0.15 mm. Hg. The product (441.8 parts) is essentially pure trimethylnitrilotripropionate having a neutralization equivalent of 273.73.

EXAMPLE 2 The procedure of Example 1 is followed but replacing theammonium acetate by 4.3 parts of lithium chloride. The same product isobtained.

EXAMPLE 3 The procedure of Example 1 is followed but the catalyst isomitted. The same product is obtained after a longer reaction time.

EXAMPLE 4 A stirred two-liter reactor equipped with a dropping funneland gas inlet tube is charged with 4.30 parts of lithium chloride. Theflask is evacuated to 5 mm. of Hg and 75 ml. (60 parts) of methanol ischarged followed by a total of 500 parts of ethyl acrylate and 27.1parts of ammonia which are added in portions over about a six-hourperiod while maintaining the temperature between 18 and 38 C. Thereaction mixture is allowed to stir for 16 hours at room temperature. Anadditional 4.3 parts of lithium chloride is added and the reactionmixture heated at a temperature of 70 C. for 3 hours and then strippedof methanol and excess ethyl acrylate at a temperature of C. and apressure of 0.35 mm. of Hg. There remains 480 parts of almost puretriethyl nitrolotripropionate having a neutralization equivalent of 315compared to theory of 317.4.

EXAMPLE 5 The procedure of Example 4 is followed but omitting thelithium chloride. The same product is obtained.

EXAMPLE 6 The procedure of Example 4 is followed but 9 parts of lithiumchloride are added only after all the ammonia is consumed.

EXAMPLE 7 A stirred two-liter reactor equipped with a dropping funneland gas inlet tube is charged with 4.30 parts of lithium chloride. Theflask is evacuated to 5 mm. of Hg and 75 parts of methanol charged,followed by a total of 430.1 parts of n-butyl acrylate and 21.4 parts ofammonia which are added in portions over about a 7-hour period whilemaintaining the temperature between 28 C. and 35 C. The reaction mixtureof di-nbutyl iminodipropionate and tri-n-butyl nitrilotripropionate isallowed to stir for 13 hours at room temperature. An additional 4.30parts of lithium chloride is added and the reaction mixture heated at atemperature of 70 to 75 C. for 3 hours and then stripped of methanol andexcess butyl acrylate at a temperature of 100 C. and a pressure of 0.25mm. of Hg. The product which is obtained is tri-n-butylnitrilotripropionate.

EXAMPLE 8 The procedure of Example 7 is followed omitting the lithiumchloride. The same product is obtained.

EXAMPLE 9 The procedure of Example 7 is followed but 9 parts of lithiumchloride are added only after all the ammonia is consumed.

EXAMPLE 10 A stirred two-liter reactor equipped with a dropping funneland gas inlet tube is charged with 4.30 parts of lithium chloride. Theflask is evacuated to 5 mm. of Hg and 150 ml. parts) of methanolcharged, followed by a total of 430.1 parts of 2-ethylhexyl acrylate and13.1 parts of ammonia which are added in portions over about a 6-hourperiod while maintaining the temperature betwen 28 and 35 C. Thereaction The procedure of Example is followed but omitting the lithiumchloride. The same product is obtained.

5 EXAMPLE 14 Theprocedure of Example 13 is followed replacing thecatalyst by zinc acetate. The same product is obtained.

EXAMPLE The procedure of Example 13 is followed replacing the catalystby aluminum triisopropoxide. The same product is obtained.

Examples 16 to 27 illustrate the preparation of various higher molecularweight nitrilotripropionates from the corresponding lower ester.

Table I.-Transesterificati0n of nitrilotripropionates Alcohol ProductEster 2 Time Pressure, Exam ples Type Moles per Catalyst, Percent (Hrs)mm. N.E.

Type Mole of Yield 0 O O R (Percent) Found Caled.

16 E Isodecyl 1. STA, 1.0 1 97-110 95.13 642. 7 653 p us 17 E Mixture ofn-octyl alco- 1. 50 STA, 2.0 5% -100 95. 15 603.4 007 hol, 45% n-deeylalcohol. plus 18 M Isooetyl 2. 00 STA, 0.75 4 -100 97. 2 562. 9 569 plus19 E Complex mixture of 1. 33 STA, .06 -103 98, 3 546. 5 549. 7

branched and straight plus chain alcohols averaging 3% 47-24 to 7 to 9carbon atoms.

20 E A mixture 01 n-Cu, OB, and 1.33 STA, .03 8 97-120 102 589. 4 573.8

C alcohols, average conlplus position of CmHr-m. 3 17-55 21 E Benzyl 2.0STA, 0.33 10 Atmv 80. 6

(Toluene azeotrope) 22 E Tetrahydrofurfuryl 2. 0 STA, 0.6 18% Atm. 77480. 2 486. 6

23 E Getyl/Stearyl averaging to 1. 0 STA, 0.2 4 85400 98 979. 2 909 17.5carbon atoms. plus 24 E 2-ethylhexyl IV 33 Aluminum triisopro- 9 95-10098+ 554 569 poxide, 0.34. plus 25 E Z-ethylhexyl H 1. 50 ZI1(OAC)2.2HO,0.17... 8% 95+ 550.9 569 26 M Oleyl 1. 50 STA, 0.33 10 100 97 975 983 27M Allyl 1. 50 STA, 0.33 12 200 98 350 353 1 NE stands for neutralizationequivalent. 2 E stands for triethyl nitrilotripropionate; M stands fortrimethyl nitrilotripropionate.

EXAMPLE 12 The procedure of Example 10 is followed but 9 parts oflithium chloride are added only after all the ammonia is consumed.

EXAMPLE 13 There are charged to a 500 ml. reactor arranged fordistillation 98.6 parts of trimethyl nitrilotripropionate, 1 86 parts ofZ-ethylhexanol, and 0.5 part of a sodium hydrogen titanium mixedalkoxide. The pressure is reduced to 99-106 mm. of Hg and the reactionmixture heated to 92-116 C. After three hours, the pressure is reducedto 41 to 50 mm. of Hg and the reaction mixture maintained at 1l8120 C.for two hours. The pressure is then reduced to 24 mm. of Hg with thetemperature at -117 C. The pressure is returned to atmospheric and 0.20part of acetic acid and 0.40 part of water are added. The mixture isheated at 8095 C. for two hours and stripped of volatile materials at atemperature of 178 C. and a pressure of 0.15 mm. of Hg. The product(202.8 parts) is tri-Z-ethylhexyl nitrilotripropionate and has arefractive index of 1.4295 at 25 C.

3 STA stands for sodium hydrogen titanium alkoxide. NOTE 1.Temperature100 0.

The esters of the invention are valuable plasticizers for polyvinylhalide resins. The term polyvinyl halide resin refers to polymerscontaining a predominant quantity, that is, a quantity greater than 50%,generally over 60%, by weight of the monomer as vinyl halide units. Thisincludes the homopolymers of the vinyl halides as well as the copolymersand interpolymers of a vinyl halide and an unsaturated monomercopolymerizable therewith. Other monomers that may be copolymerized withthe vinyl halide include the vinyl type monomers such as, for example,those having a single CH =C= group, such as vinylidene chloride, vinylchloroacetate, chlorostyrene, chlorobutadienes, etc., and thosecopolymers of such vinyl compounds and other unsaturated materialscopolymerizable therewith, for example, copolymers of a vinyl halide,such as vinyl chloride, with such materials as vinylidene chloride,vinyl esters of carboxylic acids, for example, vinyl acetate, vinylphopionate, vinyl butyrate, vinyl benzoate; esters of unsaturated acids,for example, .al kyl acrylates, such as methyl acrylate, ethyl acrylate,propyl acrylate, butyl acrylate, allyl acrylate and the correspondingesters of methacrylic acid;

vinyl aromatic compounds, for example, styrene; esters ofa,/3-unsaturated carboxylic acids, for example, the methyl, ethyl,butyl, amyl, hexyl, octyl esters of maleic, crotonic, itaconic, fumarieacids and the like. Further useful copolymers are those obtained bycopolymerization of vinyl chloride with an ester of an a,fl-unsaturateddicar-boxylic acid, such as diethyl maleate or other esters of maleic,fumaric, aconitric, itaconic acid, etc., in which 5 to 20 parts byweight of diethyl maleate or other analogous esters are used for every95 to 80 parts by weight of vinyl chloride.

When the esters of the invention are employed as plasticizers forpolyvinyl halide resins, they are ordinarily incorporated into the vinylhalide polymers by mixing the powdered resin with the liquid plasticizerfollowed by mixing and/or kneading and then by curing the mix at anelevated temperature, for example, within the range from 150 to 200 C.,on hot rolls or in a heated mixer, such as a Werner-Pfieiderer orBanbury mixer. The proportion of esters that may be employed may varyover a great range since it is dependent on the particular esters ofthis invention which is selected, the specific polyvinyl halide resin tobe plasticized, and the final degree of plasticization desired in theresin, this factor in itself being dependent on the ultimate applicationintended for the resin. With these facts in mind, one skilled in the artmay use the esters in a plasticizing amount for most purposes, thisbeing from about 5 to 100 parts, and more commonly from 20 to 60 parts,of esters per 100 parts of resin. In amounts from 60 to about 150 partsof ester per 100 parts of polyvinyl chloride resin, as from 60 to 90parts, the esters of the invention are more commonly suitable for use inorganosols and plastisols. One or more esters may be used in thepolyvinyl halide resin.

In accordance with the invention there may be employed one or moreesters of this invention in polyvinyl halide compositions; also theesters of the invention may be employed as the sole plasticizer; or theymay be employed in conjunction with conventional plasticizers, such asalkyl phthalates, alkyl phosphates, monomeric or polymeric epoxides, andother plasticizers known in the art.

With the polyvinyl halide resin, there may be incorporated variousstabilizers, fillers, dyes, pigments, and the like.

The value of the esters of the invention is further demonstrated by thefollowing illustrations.

A standard resinous composition is made up from the followingingredients.

Table II.Standard formulation Parts Polyvinyl chloride 60 Plasticizer 40Barium cadmium laurate 1.0

The resinous compositions are evaluated in accordance with tests furtherdescribed hereinafter.

1 Data are for a mixture of the plastieizer with 50% ofdi-(2-ethylhexyD- phthalate. It is evident from the data that thepolyvinyl resinous compositions are well plasticized, soft, pliable, andflexible. These properties are retained even at very low temperatures.The plasticizers also remain integrated in the resin even under hightemperature conditions; they are resistant to soap extraction and highlycompatible.

The above formulations are modified by replacing polyvinyl chloride bycopolymers of (A) 87 parts vinyl chloride: 13 parts vinyl acetate (B)parts vinyl chloridezZO parts vinylidene chloride (C) 80 parts vinylchloride:20 parts methyl acrylate (D) 95 parts vinyl chloride:5 partsvinyl isobutyl ether The resinous compositions are tested as describedabove. All compositions are supple and flexible, and they exhibit goodlow temperature flexibility allied with good resistance to hightemperature conditions.

The plasticized polyvinyl chloride compositions of the invention areuseful for many outdoor uses, such as greenhouse glazing, pond liners,ditch liners and silo covers. The compositions are well suited for manyautomotive applications, such as door panels, crash pad covers, andgasketing; for jacketing for electrical cables and many others.

The nitrilotripropionates of the invention are, furthermore, unique intheir performance in plastisols in combining excellent gelation andfusion behavior with out standing viscosity stability.

A typical plastisol composition comprising 100 parts of finely divide-dpolyvinyl chloride, 3 parts of a Ba/Cd/Zn complex stabilizer and partsof tri-2-ethylhexyl nitrilopropionate was mixed for 15 minutes in aHobart mixer and then deaerated at 28 in. of Hg for 10 minutes. Theviscosity of the plastisol was 17 poises at 60 r.p.m. after aging oneday at 77 F. A comparative composition with di-(2-ethylhexyl)phthalate('DOP) had an 18 poise/60 r.p.m. viscosity. After 21 days at 77 F., theviscosity of the composition with DOP had risen to 29. The viscosity ofthe nitrilotripropionate composition had decreased to 12 poise. Inanother experiment, at 104 F., the viscosity for thenitrilotripropionate after one day was 7 poises/60 r.p.m. Thecomposition with DOP was 20. After 21 days at 104 F., thenitrilotripropionate composition was 5; the DOP had a viscosity whichincreased to 56. Thus, while the conventional DOP composition showedgradual and perceptible gelation, the plastisol of the invention showedremarkable viscosity stability. The trem plastisol is well known in theart. See Modern Plastics, vol. 29, page 87 (1951), and US. Patent No.3,050,412, col. 3, lines 48-67, for instance.

TESTS Test 1Sh0re hardness.A Shore A durorneter, under a weight of 3pounds, is applied to the test specimens. A recording is made at onceand after 10 seconds; and the hardness is expressed by the two values,of which the first recording is the higher.

Test 2-T0rsional modulus at low temperatures.A 1%

x A1" sample is cut and mounted in a Tinius-Olsen stiffness tester,which measures the torsional modulus of plastic at various temperatures.The temperature at which a specimen has a torsional modulus of 135,000lbs/sq. in., known as T of T is determined. This roughly corresponds tothe brittle point obtained by cantilever apparatus.

Test 3Activated carbon v0latility.2" squares of weighed specimens areplaced between 2-inch layers of activated carbon in sealed glass jars,which are maintained at 90 C. for 24 hours. The specimens are removed,dusted free of carbon and reweighed.

Test 4S0apy water extractio-n.3" squares of weighed specimens areimmersed in a 1% aqueous solution of Ivory soap at 90 C. for 24 hours,after which they are thoroughly washed, dried, and reweighed.

Test 5-Compatibility.Weighed, conditioned duplicate samples, 4 inches by4 inches by 0.010 inch, are placed between two sheets of cardboard,which have been conditioned at least 15 'hours. The specimens are incontact with the white, coated side of the cardboard. Thecardboard-specimen sandwiches are placed between 5 inches by 5 inches by1 inch Wood blocks under a 3- kilogram weight. After .seven days, thespecimens are removed from the stack, conditioned, and reweighed.

Percent plasticizer loss is calculated. The cardboard sheets areexamined qualitatively for evidence of plasticizer or plasticizingstabilizer stains.

We claim:

1. A resinous vinyl chloride composition comprising a vinyl chloridepolymer selected from the group consisting of homopolymers of vinylchloride and copolymers of 50 to 95 percent by weight vinyl chloride andfrom 50 to percent by weight of a monoethylenically unsaturated monomercopolymerizable therewith, said polymer being plasticized with atrisubstituted nitrilotripropionate of the formula NOH;OH OOOR OH OHCOOR in which each of R R and R is an alkyl group of 8 carbon atoms.

2. The resinous composition of claim 1, wherein the 10nitrilotripropionate is tri(2-ethyl-hexyl)nitrilotripropomate.

3. The resinous composition of claim 1, wherein the nitrilotripropionateis triisooctyl nitrilotripropionate.

4. A vinyl plastisol composition comprising a vinyl chloride resinselected from the group consisting of homopolymers of vinyl chloride andcopolymers of to percent by weight vinyl chloride and from 50 to 5percent by weight of a monoethylenically unsaturated monomercopolymerizable therewith, and tri(2-ethylheXyl)nitrilotripropionateplasticizer.

References Cited by the Examiner UNITED STATES PATENTS 9/ 1942 Bogemannet al. 260-482 OTHER REFERENCES Mellan: The Behavior of Plasticizer-s;1961,; Pergamon Press; pages 27, 30, 31.

MORRIS LIEBMAN, Primary Examiner.

L. T. JACOBS, Assistant Examiner.

1. A RESINOUS VINYL CHLORIDE COMPOSITION COMPRISING A VINYL CHLORIDEPOLYMER SELECTED FROM THE GROUP CONSISTING OF HOMOPOLYMERS OF VINYLCHLORIDE AND COPOLYMERS OF 50 TO 95 PERCENT BY WEIGHT VINYL CHLORIDE ANDFROM 50 TO 5 PERCENT BY WEIGHT OF A MONOETHYLENICALLY UNSATURATEDMONOMER COPOLYMERIZABLE THEREWITH, SAID POLYMER BEING PLASTICIZED WITH ATRISUBSTITUTED NITRLOTRIPROPIONATE OF THE FORMULA